US9751859B2ActiveUtilityA1

Process for preparing an anti-cancer agent, 1-((4-(4-fluoro-2-methyl-1H-indol-5-yloxy)-6-methoxyquinolin-7-yloxy)methyl)cyclopropanamine, its crystalline form and its salts

90
Assignee: ADVENCHEN PHARMACEUTICALS LLCPriority: May 4, 2015Filed: May 2, 2016Granted: Sep 5, 2017
Est. expiryMay 4, 2035(~8.8 yrs left)· nominal 20-yr term from priority
A61P 35/00A61P 35/02A61P 9/10A61P 27/02A61K 2300/00A61K 39/3955C07D 401/12A61K 31/4745C07K 2317/76A61K 2039/505C07C 57/145C07K 16/22A61K 31/4709C07B 2200/13A61K 45/06A61K 31/337A61K 31/4725A61K 31/555C07C 55/10A61K 33/24A61K 33/243
90
PatentIndex Score
11
Cited by
10
References
9
Claims

Abstract

The present invention relates a new process to synthesize 1-((4-(4-Fluoro-2-methyl-1H-indol-5-yloxy)-6-methoxyquinolin-7-yloxy)methyl)cyclopropanamine (AL3818). A stable crystalline form of Al3818 has been prepared. Salts and their crystalline forms of AL3818 have been also prepared. Anti-cancer and optometric activities of AL3818 and its salts have been further tested. New process has been outlined in Scheme I.

Claims

exact text as granted — not AI-modified
What is claimed is: 
     
       1. A crystalline form of 1-((4-(4-Fluoro-2-methyl-1H-indol-5-yloxy)-6-methoxyquino-lin-7-yloxy)methyl)cyclopropanamine of AL3818 exhibiting at least one of following characters:
 a melting point at 208° C.-210° C.; 
 a DSC Melting Range (Endo): 207-220° C. with Peak Temp=216° C., pattern shown in  FIG. 1 ; 
 a TGA thermogram that doesn't exhibit significant weight loss until at 205-215° C., pattern shown in  FIG. 2 . 
 
     
     
       2. A crystalline form of 1-((4-(4-Fluoro-1-methyl-1H-indol-5-yloxy)-6-methoxyquino-lin-7-yloxy)methyl)cyclopropanamine according  claim 1  exhibiting a XRPD having pattern shown in  FIG. 3  comprising 10 characteristic peaks with intensity % greater than 10% expressed in d values and angles as follows: 
       
         
           
                 
                 
                 
               
                     
                 
                     
                   Angle 
                   d value 
                 
                     
                 
                     
                 
                 
                 
                 
               
                     
                   13.344 
                   6.62986 
                 
                     
                   15.858 
                   5.58405 
                 
                     
                   16.799 
                   5.27326 
                 
                     
                   17.640 
                   5.02377 
                 
                     
                   18.770 
                   4.72373 
                 
                     
                   20.650 
                   4.29771 
                 
                     
                   21.633 
                   4.10463 
                 
                     
                   23.087 
                   3.84934 
                 
                     
                   25.128 
                   3.54112 
                 
                     
                   26.607 
                   3.34755. 
                 
                     
                 
             
                
                
                
               
               
                
               
            
             
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
       3. A crystalline form of 1-((4-(4-Fluoro-2-methyl-1H-indol-5-yloxy)-6-methoxyquino-lin-7-yloxy)methyl)cyclopropanamine according  claim 1  exhibiting a XRPD having pattern shown in  FIG. 3  comprising 26 characteristic peaks with all intensity % expressed in d values and angles as follows: 
       
         
           
                 
                 
                 
                 
                 
               
                     
                     
                 
                     
                     
                     
                   d  
                   Intensity  
                 
                     
                   NO. 
                   Angle 
                   value 
                   (%) 
                 
                     
                     
                 
                     
                 
                 
                 
                 
                 
                 
               
                     
                   1 
                   10.892 
                   8.11623  
                   2.1 
                 
                     
                   2 
                   11.589 
                   7.62991  
                   6.1 
                 
                     
                   3 
                   12.195 
                   7.25174  
                   5.9 
                 
                     
                   4 
                   13.344 
                   6.62986 
                   36.2 
                 
                     
                   5 
                   15.858 
                   5.58405 
                   31.5 
                 
                     
                   6 
                   16.799 
                   5.27326  
                   77.9 
                 
                     
                   7 
                   17.640 
                   5.02377 
                   18.8 
                 
                     
                   8 
                   18.770 
                   4.72373  
                   11.9 
                 
                     
                   9 
                   19.987 
                   4.43884  
                   7.2 
                 
                     
                   10 
                   20.650 
                   4.29771  
                   42.0 
                 
                     
                   11 
                   21.633 
                   4.10463  
                   15.3 
                 
                     
                   12 
                   23.087 
                   3.84934  
                   100.0 
                 
                     
                   13 
                   24.356 
                   3.65157  
                   3.5 
                 
                     
                   14 
                   25.128 
                   3.54112 
                   14.6 
                 
                     
                   15 
                   25.669 
                   3.46768 
                   3.8 
                 
                     
                   16 
                   26.607 
                   3.34755 
                   18.0 
                 
                     
                   17 
                   26.607 
                   3.34755 
                   3.1 
                 
                     
                   18 
                   29.050 
                   3.07132 
                   5.7 
                 
                     
                   19 
                   29.797 
                   2.99602 
                   1.5 
                 
                     
                   20 
                   30.681 
                   2.91167 
                   4.3 
                 
                     
                   21 
                   31.853 
                   2.80718 
                   1.2 
                 
                     
                   22 
                   33.524 
                   2.67095 
                   2.8 
                 
                     
                   23 
                   34.789 
                   2.57667 
                   2.6 
                 
                     
                   24 
                   35.873 
                   2.50131 
                   2.2 
                 
                     
                   25 
                   37.391 
                   2.40313 
                   3.9 
                 
                     
                   26 
                   38.637 
                   2.32846 
                   1.4. 
                 
                     
                     
                 
             
                
                
                
                
               
               
                
               
            
             
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
       4. A pharmaceutical composition that comprises as an active ingredient a compound as defined in  claim 1  of the compound and a pharmaceutically acceptable carrier. 
     
     
       5. A method of treating an optometric disease, said method comprising administering a compound as defined in  claim 1 . 
     
     
       6. A method of treating as claimed in  claim 5 , wherein an optometric disease is AMD and the combing anti-VEGF antibody is ranibizumab, or the VEGF trap is aflibercep. 
     
     
       7. A method of treating an optometric disease, said method comprising administering a pharmaceutical composition comprising a compound as defined in  claim 1  and pharmaceutically acceptable excipients to a subject in need thereof. 
     
     
       8. A method of treating an optometric disease, said method comprising administering a pharmaceutical composition comprising the compound as defined  claim 1  with an anti-VEGF antibody or VEGF trap to a subject in need thereof. 
     
     
       9. A process to synthesize 1-((4-(4-Fluoro-2-methyl-1H-indol-5-yloxy)-6-methoxyquino-lin-7-yl-oxy)methyl)cyclopropanamine (AL3818) according to  claim 1  where AL3818 can be prepared according to Process A1 when R is H by deprotecting intermediate (Z-1) with HCOONH4 (ammonium formate) and Pd/C in an alcoholic solvent at 25° C.-80° C. for 0.1-4 hours (Z-1) can be prepared by reacting intermediate (X1) with (Y1-1) at the presence of KI or NaI with K 2 CO 3  in acetone or DMF at a temperature of 60° C.−160° C. for 2-24 hours.

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